TW201622977A - Antistatic sheet, and packaging material and electronic device including same - Google Patents

Abstract

The present invention provides a novel antistatic sheet having a high gas barrier property, a high water-vapor barrier property, and an antistatic property, and a packaging material and an electronic device which include the antistatic sheet. The present invention pertains to an antistatic sheet having a multilayer structure including a substrate (X), a layer (Z) containing aluminum atoms, and a layer (Y). The layer (Y) contains a polymer (A) having vinylphosphonic acid units, and the surface electric resistivity of the layer (Y) is 1.0*10<SP>6</SP> to 4.0*10<SP>13</SP> [Omega]/sq inclusive.

Description

Antistatic sheet and packaging material and electronic device therewith

The present invention relates to an antistatic sheet and a packaging material and an electronic device therewith.

A laminate in which a gas barrier layer containing aluminum or aluminum oxide as a constituent component is formed on a plastic film has been known from the past. Such a laminate is used as a packaging material for protecting an article (for example, food) which is easily deteriorated by oxygen. Most of these gas barrier layers are formed on a plastic film by a dry process such as a Vapor phase epitaxy method or a chemical vapor phase epitaxy method. The aluminum vapor-deposited film is also light-shielding in addition to gas barrier properties, and is mainly used as a packaging material for dry foods. On the other hand, the alumina-deposited film having transparency can be visually recognized, and has a feature that it can be checked by a foreign object of a metal detector or heated by a microwave oven. Therefore, the film was initially packaged as a retort food and used as a packaging material in a wide range of applications.

As a gas barrier layer containing aluminum, a transparent gas barrier layer composed of, for example, an aluminum atom, an oxygen atom, and a sulfur atom is disclosed in Patent Document 1. Patent Document 1 discloses that it is formed by reactive sputtering. The method of the transparent gas barrier layer.

Further, a transparent gas barrier layer composed of a reaction product of an alumina particle and a phosphorus compound is disclosed in Patent Document 2. As one of methods for forming the gas barrier layer, a coating liquid containing alumina particles and a phosphorus compound is applied onto a plastic film, and a method of drying and heat treatment is disclosed in Patent Document 2.

However, the conventional gas barrier layer is excellent in gas barrier properties, but may have a large surface electrical resistivity. In such a case, the application of gas barrier properties to applications requiring antistatic properties is difficult. In the past, the vertical bag-filled thin-film bag was filled with dried squid, and the contents adhered to the inner surface and the outer surface of the bag due to static electricity. When heat-sealing, there was a powdery body in the heat-sealed portion or a contamination sealing machine. Case. Further, when the bag is opened, the dried squid cannot be smoothly taken out, and the dried squid is attached to the outer periphery of the bag.

Patent Document 3 discloses a gas barrier in-mold label having an antistatic layer. Patent Document 3 describes that the in-mold label has water vapor barrier properties. However, in Patent Document 3, it is not described whether or not the in-mold label has oxygen barrier properties.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-251732

[Patent Document 2] International Publication No. 2011/122036

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-5836

One of the objects of the present invention is to provide a novel antistatic sheet having high gas barrier properties and high water vapor barrier properties and antistatic properties, and a packaging material and an electronic device therewith.

As a result of intensive studies, the present inventors have found that the above object can be attained by providing an antistatic sheet having a multilayer structure including a specific layer, and the present invention has been completed.

The present invention provides an antistatic sheet characterized by an antistatic sheet comprising a multilayer structure comprising a substrate (X), a layer (Z) containing aluminum atoms, and a layer (Y), the layer (Y) contains a polymer (A) having a phosphonic acid unit, and the surface electrical resistivity of the layer (Y) is 1.0 × 10 ⁶ Ω/sq or more and 4.0 × 10 ¹³ Ω/sq or less.

In the antistatic sheet of the present invention, the polymer (A) having a phosphonic acid unit may be a polymer (Aa) having a vinylphosphonic acid unit.

In the antistatic sheet of the present invention, at least one of the aforementioned layer (Z) and the layer (Y) may be adjacently disposed.

In the antistatic sheet of the present invention, the layer (Z) may include a layer (Z1) containing a reaction product (E), and the reaction product (E) is a metal oxide (C) containing an aluminum atom and a phosphorus compound ( D) The reaction product obtained by the reaction, in the infrared absorption spectrum of the layer (Z1), the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 may be in the range of 1,080 to 1,130 cm ^-1 .

In the antistatic sheet of the present invention, the layer (Z) may be provided with a vapor deposited layer (Z3) of alumina.

In the antistatic sheet of the present invention, the oxygen transmission rate under conditions of 20 ° C and 85% RH may be 2 mL / (m ² .day.atm) or less.

The present invention provides a packaging material. The packaging material comprises the antistatic sheet of the present invention. Further, the present invention provides an electronic device. The electronic device comprises the antistatic sheet of the present invention.

According to the present invention, an antistatic sheet excellent in gas barrier properties and water vapor barrier properties and excellent in antistatic property can be obtained. Further, the antistatic sheet of the present invention does not cause an antistatic property, and the appearance is poor due to adhesion of fine powder on the surface.

10‧‧‧Vertical bag filling and sealing bag

11‧‧‧Multilayer structure

11a‧‧‧End

11b‧‧‧ body part

11c‧‧‧ surrounding parts

20‧‧‧ flat pouch

30‧‧‧vacuum heat insulator

31‧‧‧ core material

40‧‧‧Electronic devices

41‧‧‧Electronic device body

42‧‧‧ Sealing material

43‧‧‧Protective sheet (multilayer structure)

Fig. 1 is a schematic view showing an example of a vertical bag-filling sealed bag according to the present invention.

Fig. 2 is a schematic view showing an example of a flat pouch by the present invention.

Fig. 3 is a schematic view showing an example of a vacuum heat insulator according to the present invention.

[Fig. 4] shows a part of an example of an electronic device by the present invention Sectional view.

The present invention will be described below by way of examples. In the following description, the examples, conditions, methods, numerical ranges, and the like are exemplified, but the present invention is not limited to such an example. Further, the exemplified substances may be used alone or in combination of two or more kinds unless otherwise specified.

Unless otherwise stated, in this specification, the meaning of the description of "layering a specific layer on a specific member (substrate, layer, etc.)" is not the case of laminating the specific layer in contact with the member. In addition, it also includes the case of holding other layers and laminating the specific layer above the member. The description of "forming a specific layer on a specific member (substrate, layer, etc.)" and "disposing a specific layer on a specific member (substrate, layer, etc.)" is also the same. In addition, unless otherwise stated, the meaning of the description of the coating liquid (coating liquid or the like) on a specific member (base material, layer, etc.) is included in addition to directly applying the liquid to the member. The application of the liquid to other layers formed on the member.

In this specification, the term "layer (Y)" and the symbol (Y) have a case where the layer (Y) is distinguished from other layers. Unless otherwise stated, there is no technical meaning in symbol (Y). The same applies to the substrate (X), the layer (Z), the polymer (A), and other symbols. However, as in the case of a hydrogen atom (H), it is very clear that a particular element is indicated.

[Anti-static sheet]

The antistatic sheet of the present invention can be constituted substantially only by a multilayer structure. Further, in the antistatic sheet of the present invention, as long as the multilayer structure has the layer (Y), even if the layer (Y) is not the outermost layer, it can also have high gas barrier properties and high water vapor barrier properties and antistatic properties. It is not limited to the multilayer structure in which the layer (Y) is the outermost layer.

[Multilayer structure]

The multilayer structure system of the present invention comprises a substrate (X), a layer (Z) containing aluminum atoms, and a layer (Y). In the following description, the term "multilayer structure" means a multilayer structure including a substrate (X) and a layer (Z) and a layer (Y) unless otherwise specified. Layer (Y) comprises a polymer (A) having a phosphonic acid unit. The surface electrical resistivity of the layer (Y) is 1.0 × 10 ⁶ Ω/sq or more and 4.0 × 10 ¹³ Ω/sq or less. In a preferred embodiment, the layer (Y) is disposed on a surface of at least one side of the multilayer structure.

[Substrate (X)]

The material of the substrate (X) is not particularly limited, and a substrate composed of various materials can be used. Examples of the material of the base material (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as cloths and papers; wood; and glass. Among these, thermoplastic resin and paper are preferred. A preferred example of the substrate (X) includes at least one selected from the group consisting of a thermoplastic resin film layer and a paper layer. The substrate (X) may be a composite composed of a plurality of materials, or may be a single layer or a complex Floor.

The form of the substrate (X) is not particularly limited, and may be a layered substrate such as a film or a sheet, or may be a molded body having a three-dimensional shape such as a sphere, a polyhedron or a catheter. Among these, the layered base material is particularly useful in the case of using a multilayer structure (laminated structure) in a packaging material, a solar cell member, or the like. The use of the multilayer structure of the substrate (X) is excellent in the processability of the packaging material or many properties sought when used as a packaging material.

Examples of the thermoplastic resin used for the substrate (X) include polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate and polyethylene-2,6-naphthalate; Polybutylene terephthalate or a polyester resin such as a copolymer; a polyamide resin such as nylon-6, nylon-66 or nylon-12; polyvinyl alcohol or ethylene-vinyl alcohol a hydroxyl group-containing polymer such as a copolymer; polystyrene; poly(meth)acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyallyl ester; regenerated cellulose; polyimine; Ether quinone imine; polyfluorene; polyether oxime; polyether ether ketone; ionic polymer resin. When the multilayer structure is used for a packaging material, the material of the substrate (X) is preferably selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66. At least one thermoplastic resin in the group.

When the film composed of the thermoplastic resin is used as the substrate (X), the substrate (X) may be a drawn film or a non-drawn film. Since the obtained multilayer structure is excellent in processing suitability (printing, lamination, etc.), it is preferable to use a drawn film, particularly a biaxially drawn film. The two-axis drawing film can be a simultaneous two-axis drawing method, a sequential two-axis drawing method, and a tubular A biaxially drawn film produced by any of the methods of drawing.

Examples of the paper used as the substrate (X) include kraft paper, top paper, mold paper, glass paper, parchment paper, synthetic paper, white paper, Manila ball, milk carton base paper, Cup base paper, ivory paper, etc. A multilayer structure for a paper container can be obtained by using paper on a substrate.

When the base material (X) is in the form of a layer, the thickness thereof is preferably in the range of 1 to 1,000 μm, more preferably 5 to 500 μm from the viewpoint of improving the mechanical strength or workability of the obtained multi-layer structure. The range is more preferably in the range of 9 to 200 μm.

[layer (Y)]

Layer (Y) comprises a polymer (A) having a phosphonic acid unit. The polymer (A) having a phosphonic acid unit which is a polymer contained in the layer (Y) is sometimes referred to as "polymer (A)" hereinafter. The content of the polymer (A) in the layer (Y) is in the range of 50 to 100% by mass (for example, 95% by mass or more) based on the mass of the layer (Y) (100% by mass).

[Polymer acid unit (A)]

The polymer (A) may be composed only of a phosphonic acid unit, and may also contain other monomer units. The ratio of the phosphonic acid unit occupied by the entire constituent unit of the polymer (A) may range from 50 mol% to 100 mol%, and may range from 80 mol% to 100 mol%.

The polymer (A) is a polymer having a phosphonic acid unit, preferably A homopolymer or copolymer of an alkenylphosphonic acid. The alkenylphosphonic acid is a phosphonic acid having an alkenyl group as a substituent, and is represented by the following general formula [III].

R ⁵ -P(=O)(OH) ₂ [III]

In the formula, R ⁵ may have an alkenyl group having 2 to 30 (for example, 2 to 10) carbon atoms of the substituent. In the alkenyl group, one or more oxycarbonyl groups may be contained in the molecular chain, and a part of the carbon chain may constitute a carbocyclic ring.

In the case of the aforementioned alkenyl group, a hydrocarbon chain having a carbon-carbon double bond (for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a 2-methyl group) is included. 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-hexenyl, 1,3-hexadiene, 1,5-hexane Alkene, etc.). Further, examples of the carbocyclic ring having the alkenyl group include a benzene ring, a naphthalene ring, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, and a cyclopentene ring. Further, in addition to the hydrocarbon chain having a carbon-carbon double bond on the carbocyclic ring, one or more saturated hydrocarbon chains (for example, a methyl group, an ethyl group, a propyl group or the like) may be bonded.

Examples of the monomer which can be suitably used in the alkenylphosphonic acid of the present invention include alkenylphosphonic acid such as vinylphosphonic acid and 2-propene-1-phosphonic acid; 4-vinylbenzylphosphonic acid, 4- An alkenyl aromatic phosphonic acid such as vinyl phenylphosphonic acid. Among them, an alkenylphosphonic acid is preferred, and a vinylphosphonic acid is more preferred.

As the polymer (A), a polymer (Aa) having a vinylphosphonic acid unit is preferred. Examples of the polymer (Aa) include poly(vinylphosphonic acid) and vinylphosphonic acid. A methacrylic acid copolymer or the like. Among these, poly(vinylphosphonic acid) is preferred from the viewpoint of obtaining high antistatic property. The molecular weight of the polymer (A) is not particularly limited, and the number average molecular weight thereof may be 5,000~ A range of 100,000.

The polymer (A) can be obtained by polymerizing a monomer containing at least one of a phosphonic acid. The polymer (A) may be a copolymer of a phosphonic acid and another vinyl monomer. Examples of other vinyl monomers copolymerizable with the phosphonic acid include (meth)acrylic acid, (meth)acrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nuclear-substituted styrenes, and alkyl groups. Vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, anhydrous maleic acid, fumaric acid, itaconic acid, malayan Imine, phenyl maleimide, and the like. Among these, (meth)acrylates, acrylonitrile, styrene, maleimide, and phenylmaleimide are preferred.

In the antistatic sheet of the present invention, since the surface electrical resistivity of the layer (Y) existing on the surface is in a specific range, excellent characteristics are exhibited. Electrical resistivity of the surface layer (Y) of 1.0 × 10 ⁶ Ω / sq or more and 4.0 × 10 ¹³ Ω / sq or less, the antistatic sheet exhibits excellent antistatic properties. The surface electrical resistivity of the layer (Y) may be 1.0 × 10 ⁶ Ω/sq or more and 3.0 × 10 ¹² Ω/sq or less.

In general, the greater the polarity of the molecule, the lower the electrical resistance of the surface of the layer containing the molecule. When the polarity of the molecule is large, the charge in the molecule is localized, and it is divided into a portion where the charge is positive and a portion where the charge is negative. Therefore, the layer containing a molecule having a large polarity increases conductivity and reduces surface resistance. It is considered that the polymer (A) having a phosphonic acid unit exhibits high antistatic property by using the layer (Y) containing the polymer (A) because of its high polarity.

In particular, when the layer (Y) is adjacent to the layer (Z), a part of the phosphonic acid unit in the polymer (A) is reacted with the aluminum atom in the layer (Z), The possibility of exhibiting higher antistatic properties. The electronegativity of Pauling is 2.29 for phosphorus atoms, 3.44 for oxygen atoms, 2.20 for hydrogen atoms, and 1.61 for aluminum atoms. The difference in electronegativity between the oxygen atom and the hydrogen atom is 1.24, and the difference in electronegativity between the oxygen atom and the aluminum atom is 1.83. Therefore, a part of the phosphonic acid group in the layer (Y) is further reacted with the aluminum atom in the layer (Z), the charge shift is further increased, and the conductivity is increased (that is, the electrical resistance is reduced). Therefore, when the layer (Y) is adjacent to the layer (Z), there is a possibility that a high antistatic property is obtained in particular. Further, the value of the negative charge of Pauling of each atom is a value described in Table 3 of the following Reference 1.

Reference 1: A. L. Allred, Journal of Inorganic and Nuclear Chemistry, Vol. 17, pp. 215-221 (1961)

The mechanism by which the antistatic effect is produced by the constitution of the present invention has not been clarified until now.

The surface electrical resistivity of the layer (Y) can be increased or decreased by the polarity of the molecules constituting the layer (Y). The surface electrical resistivity of the layer (Y) can be increased, for example, by reducing the amount of the phosphonic acid unit in the polymer (A) or by adding a nonionic compound (for example, polyvinyl alcohol) to the layer (Y). Further, when the polymer (A) is polymerized, the surface electrical resistivity of the layer (Y) can be lowered by substituting the phosphonic acid in the polymer (A) with a phosphonate (for example, sodium vinylphosphonate). Further, even if an ionic compound (for example, a quaternary ammonium salt) is added to the layer (Y), the surface electrical resistivity of the layer (Y) can be lowered. Further, even if the amount of the phosphonic acid unit in the polymer (A) is increased, the surface electrical resistivity of the layer (Y) can be lowered.

[Polymer (B)]

The layer (Y) may further comprise a polymer (B). The polymer (B) has a hydroxyl group and/or a carboxyl group. By including the polymer (B), the adhesion of the antistatic sheet of the present invention to other layers can be improved. In general, the polymer (B) does not contain a functional group containing a phosphorus atom. In the layer (Y), the mass ratio of the polymer (A) to the polymer (B) is not particularly limited, and may range from 15:85 to 100:0, although it may range from 15:85 to 99:1. , preferably in the range of 20:80 to 99:1, more preferably in the range of 60:40 to 99:1, more preferably in the range of 50:50 to 85:15 or 55:45 to 75:25. range. When the mass ratio of the polymer (A) to the polymer (B) is in the above range, both the antistatic property and the adhesion of other layers can be achieved.

Examples of the polymer (B) having a hydroxyl group and/or a carboxyl group include a polyvinyl alcohol, a modified polyvinyl alcohol having 1 to 50 mol% of an α-olefin unit having 4 or less carbon atoms, and a polyethylene shrinkage. a polyvinyl alcohol-based polymer such as an aldehyde (polyvinyl butyral) or the like; a polysaccharide such as cellulose or starch; a polyhydroxyethyl (meth) acrylate, a poly(meth) acrylate, or an ethylene-( (meth)acrylic polymer such as methyl)acrylic acid copolymer; hydrolyzate of ethylene-anhydrous maleic acid copolymer, hydrolyzate of styrene-anhydrous maleic acid copolymer, isobutylene-hydrogenic acid cross-copolymerization A maleic acid polymer or the like which is a hydrolyzate or the like. Among these, a polyvinyl alcohol-based polymer is preferable, and specifically, a polyvinyl alcohol and a modified polyvinyl group containing 1 to 15 mol% of an α-olefin unit having 4 or less carbon atoms or less are preferable. alcohol.

The polymer (B) may be a monomer having a hydroxyl group and/or a carboxyl group (for example, acrylic acid or the like), or may be reacted by polymerization (for example, hydrolysis reaction) A homopolymer of a monomer having a hydroxyl group and/or a carboxyl group (for example, vinyl acetate, acrylate, etc.) may be a copolymer of two or more kinds of monomers, and may be a monomer having a hydroxyl group and/or a carboxyl group. A copolymer that does not have a monomer of the group. Further, as the polymer (B), two or more kinds of polymers (B) may be used in combination.

The molecular weight of the polymer (B) is not particularly limited, but in order to obtain a multilayer structure having more excellent gas barrier properties and mechanical properties (falling strength, etc.), the number average molecular weight of the polymer (B) is preferably More than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (B) is not particularly limited and is, for example, 1,500,000 or less.

The layer (Y) may be composed only of the polymer (A), or may be composed only of the polymer (A) and the polymer (B), and may further contain other components (for example, an ionic compound). The content of the other components in the layer (Y) is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, particularly preferably 5% by mass or less, and may be 0. % by mass (excluding other ingredients). Typically, layer (Y) does not contain the aluminum atoms contained in layer (Z). In other words, the usual layer (Y) is different from the layer (Z) in that it does not substantially contain the aluminum atoms contained in the layer (Z).

The content of the polymer (B) in the layer (Y) is based on the mass of the layer (Y) (100% by mass), preferably 85% by mass or less, from the viewpoint of retaining the appearance of the multilayer structure. More preferably, it is 50 mass% or less, further preferably 20 mass% or less, and particularly preferably 10 mass% or less. The polymer (B) may or may not react with the components of the layer (Y).

Layer (Y) thickness of each layer, from the multilayer structure of the present invention From the viewpoint of good flexural flexibility, it is preferably 0.003 μm or more. Although the upper limit of the thickness of the layer (Y) is not particularly limited, the effect of improving the flex resistance at 1.0 μm or more is saturated. Therefore, the upper limit of the total thickness of the layer (Y) is preferably 1.0 μm from the viewpoint of economy. The thickness of the layer (Y) is more preferably 0.005 to 0.90 μm, still more preferably 0.01 to 0.60 μm. The thickness of the layer (Y) can be controlled by the concentration of the coating liquid (S) described later by the formation of the layer (Y) or a coating method thereof.

[layer (Z)]

The multilayer construction system of the present invention comprises a layer (Z) having aluminum atoms. It is preferred that the layers (Y) and (Z) are laminated in an adjacent manner (e.g., contact). In other words, in the multilayer structure of the present invention, at least one of the layers (Z) and (Y) is preferably disposed adjacent to each other. In a preferred embodiment, at least one of the layers (Y) and (Z) are arranged in the order of layer (Y)/layer (Z) from the surface side of the multilayer structure.

The layer (Z) may be a layer (Z1) comprising a reaction product (E) obtained by reacting a metal oxide (C) containing an aluminum atom with a phosphorus compound (D). Here, the metal oxide (C) and the phosphorus compound (D) are further reacted with other compounds, and the resulting compound is also contained in the reaction product (E). Further, the layer (Z) may be a layer (Z2) which is an evaporated layer of aluminum. Further, the layer (Z) may be a vapor deposited layer containing an oxide of an aluminum atom, or may be a layer (Z3) which is a vapor deposited layer of alumina.

[layer (Z1)]

As a structure of the reaction product (E) contained in the layer (Z1), for example, it can be listed The particles of the metal oxide (C) are each a structure in which a phosphorus atom derived from the phosphorus compound (D) is bonded. The form in which the phosphorus atom is bonded is a form in which a bond is formed by a group containing a phosphorus atom, for example, a form in which a group is bonded through a group of atoms, and the group does not include a metal atom containing a phosphorus atom. Further, the layer (Z1) may partially contain a metal oxide (C) and/or a phosphorus compound (D) which are not related to the reaction.

In the layer (Z1), the molar ratio of the metal atom constituting the metal oxide (C) to the phosphorus atom derived from the phosphorus compound (D) is preferably [the metal atom constituting the metal oxide (C)]: [source The range from the phosphorus atom of the phosphorus compound (D)] = 1.0: 1.0 to 3.6: 1.0, more preferably in the range of 1.1: 1.0 to 3.0: 1.0. Outside of this range, gas barrier properties are reduced. The molar ratio at the layer (Z1) can be adjusted by the mixing ratio of the metal oxide (C) and the phosphorus compound (D) in the coating liquid for forming the layer (Z1). The molar ratio in the layer (Z1) is usually the same as the ratio in the coating liquid.

In the infrared absorption spectrum of the layer (Z1), the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 is preferably in the range of 1,080 to 1,130 cm ^-1 . In the process of reacting the metal oxide (C) with the phosphorus compound (D) to form the reaction product (E), the metal atom (M) derived from the metal oxide (C) and the phosphorus compound (D) are derived. The phosphorus atom (P), through the oxygen atom (O), forms a bond represented by MOP. As a result, in the infrared absorption spectrum of the reaction product (E), a characteristic absorption band derived from the bond is generated. As a result of the study by the inventors, it was found that when the characteristic absorption band was observed in the region of 1,080 to 1,130 cm ^-1 according to the bond of MOP, the obtained multilayer structure exhibited excellent gas barrier properties. In particular, in the characteristic absorption band, it is understood that, in general, when the absorption from the bond of various atoms and oxygen atoms is observed to be the strongest absorption in the region of 800 to 1,400 cm ^-1 , the obtained multilayer structure is further excellent. Gas barrier properties.

On the other hand, when a metal compound such as a metal alkoxide or a metal salt and a phosphorus compound (D) are mixed in advance and then hydrolyzed and condensed, a metal atom derived from the metal compound and a phosphorus atom derived from the phosphorus compound (D) are obtained. It is mixed into a complex that is almost homogeneously reacted. In this case, in the infrared absorption spectrum, the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 is deviated outward from the range of 1,080 to 1,130 cm ^-1 .

Infrared layer (Z1) of the absorption spectrum, the half width of the maximum area of 800 ~ 1,400cm ^-1 absorption band, from the viewpoint of gas barrier properties of the multilayered structure obtained from the point of view, is preferably 200cm ^-1 or less, more It is preferably 150 cm ^-1 or less, more preferably 100 cm ^-1 or less, and particularly preferably 50 cm ^-1 or less.

The infrared absorption spectrum of the layer (Z1) can be measured by the method described in the examples. However, when it is not possible to measure by the method described in the examples, it is possible to scrape off the layer (Z1) from the multilayer structure by the reflection measurement such as the reflection absorption method, the external reflection method, or the attenuation total reflection method. The measurement is carried out by a method such as measurement, but is not limited thereto.

The metal oxide (C) may be a hydrolysis condensate of the compound (G) containing a metal atom (M) whose bond is hydrolyzable. An example of the characteristic base includes R ¹ of the general formula [I] described later. The hydrolysis condensate of the compound (G) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of the compound (G) may be referred to as "metal oxide (C)". That is, in this specification, "metal oxide (C)" can be interpreted as "hydrolysis condensate of compound (G)", and "hydrolysis condensate of compound (G)" can also be interpreted as "metal oxide"(C)".

The thickness of the layer (Z1) (when the multilayer structure has two or more layers (Z1), the total thickness of each layer (Z1)) is preferably in the range of 0.05 μm to 4.0 μm, more preferably 0.1 μm to 2.0. The range of μm. By the thin layer (Z1), the dimensional change of the multilayer structure at the time of processing such as printing or lamination can be suppressed. Further, since the flexibility of the multilayer structure is increased, the mechanical properties thereof can be brought close to the mechanical properties of the substrate itself. When the multilayer structure of the present invention has two or more layers (Z1), the thickness of each layer of the layer (Z1) is preferably 0.05 μm or more from the viewpoint of gas barrier properties. The thickness of the layer (Z1) can be controlled by the concentration of the coating liquid (T) described later by the formation of the layer (Z1) or a coating method thereof.

The thickness of the layer (Z1) can be measured by a scanning electron microscope or a transmission electron microscope. Further, the layer (Y) and other layers can also be measured by the same method.

[Metal Oxide (C)]

The metal atom constituting the metal oxide (C) (sometimes referred to as "metal atom (M)") is a metal atom selected from at least one of metal atoms belonging to Groups 2 to 14 of the periodic table. But at least contains aluminum atoms. The metal atom (M) may be an aluminum atom alone or a metal atom other than the aluminum atom. Further, as the metal oxide (C), two or more kinds of metal oxides (C) may be used in combination.

The proportion of the aluminum atom occupied by the metal atom (M) is usually 50 mol% or more, and may be in the range of 60 mol% to 100 mol%, or 80 mol% to 100 mol%. Examples of the metal oxide (C) include metal oxides produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method.

[compound (G)]

The obtained multilayer structure is excellent in gas barrier property, and the compound (G) is preferably a compound (G1) containing at least one of the following general formula [I].

AI(R ¹ ) _k (R ² ) _3-k [I]

In the formula, R ¹ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a carbon number 2 to 9 which may have a substituent. a decyloxy group, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a β-diketone group having 5 to 15 carbon atoms which may have a substituent, or a carbon number of 1 to 9 which may have a substituent Dimethylmethyl group of fluorenyl. R ² may have an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have a substitution An aryl group having a carbon number of 6 to 10. k is an integer from 1 to 3. When R ¹ is a plural, R ¹ may be the same or different from each other. When R ² is in the plural, R ² may be the same or different from each other.

The compound (G) may contain, in addition to the compound (G1), at least one compound (G2) represented by the following general formula [II].

M ¹ (R ³ ) _m (R ⁴ ) _nm [II]

In the formula, M ¹ is a metal atom other than an aluminum atom, and the atom belongs to at least one metal atom of a metal atom of Groups 2 to 14 of the periodic table. R ³ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), NO ₃ , an alkoxy group having a carbon number of 1 to 9 which may have a substituent, and a carbon number of 2 to 9 which may have a substituent. An oxy group, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a β-diketone group having 5 to 15 carbon atoms which may have a substituent, or a mercapto group having 1 to 9 carbon atoms which may have a substituent Dimethylmethyl. R ⁴ is an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have a substitution An aryl group having a carbon number of 6 to 10. m is an integer from 1 to n. n is equivalent to the valence of M ¹ . When R ³ is in the plural, R ³ may be the same or different from each other. When R ⁴ is in the plural, R ⁴ may be the same or different from each other.

Examples of the alkoxy group of R ¹ and R ³ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. Tert-butoxy, benzyloxy, diphenylmethoxy, triphenylmethoxy, 4-methoxybenzyloxy, methoxymethoxy, 1-ethoxyethoxy, benzyloxy A methoxy group, a 2-trimethyl decyl ethoxy group, a 2-trimethyl decyl ethoxy methoxy group, a phenoxy group, a 4-methoxyphenoxy group, or the like.

Examples of the decyloxy group of R ¹ and R ³ include an ethoxycarbonyl group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, and an isobutyl group. Alkoxycarbonyl group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, n-octylcarbonyloxy group and the like.

Examples of the alkenyloxy group for R ¹ and R ³ include an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, a 1-methyl-2-propenyloxy group, and a 3-butenyloxy group. 2-methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-3-butenyloxy, 1,2-dimethyl 2-propenyloxy, 1,1-dimethyl-2-propenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 2-methyl 3-butenyloxy, 3-methyl-3-butenyloxy, 1-vinyl-2-propenyloxy, 5-hexenyloxy and the like.

Examples of the β-diketone group of R ¹ and R ³ include a 2,4-pentanedione group (dionato) and a 1,1,1-trifluoro-2,4-pentanedione group; 1,1,5,5,5-hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-butyl An alkanedione group, a 2-methyl-1,3-butanedione group, a 2-methyl-1,3-butanedione group, an acetonate or the like.

Examples of the fluorenyl group of the dimercaptomethyl group of R ¹ and R ³ include a methyl group, an ethyl group, a propanoyl group, a Butanoyl group, a Pentanoyl group, and An aliphatic fluorenyl group having 1 to 6 carbon atoms such as a mercapto group; an aromatic fluorenyl group such as a benzamidine group or a toluoyl group;

Examples of the alkyl group of R ² and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentylene group. Base, isopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

Examples of the aralkyl group of R ² and R ⁴ include a benzyl group and a phenylethyl group (phenethyl group).

Examples of the alkenyl group of R ² and R ⁴ include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 3-butenyl group, a 2-butenyl group, a 1-butenyl group, and a 1- Methyl-2-propenyl, 1-methyl-1-propenyl, 1-ethyl-1-vinyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 3- Methyl-2-butenyl, 4-pentenyl and the like.

Examples of the aryl group of R ² and R ⁴ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of the substituent of R ¹ , R ² , R ³ and R ⁴ include an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and n. -butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropoxy, cyclobutoxy, ring Alkoxy group having 1 to 6 carbon atoms such as pentyloxy group or cyclohexyloxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, Isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentyloxycarbonyl An alkoxycarbonyl group having 1 to 6 carbon atoms; an aromatic hydrocarbon group such as a phenyl group, a tolyl group or a naphthyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and a carbon number of 1 to 6 a arylalkyl group having 7 to 10 carbon atoms; an aralkyloxy group having 7 to 10 carbon atoms; an alkylamino group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; .

R ^{1 is} preferably a halogen atom, NO ₃ , an alkoxy group having 1 to 6 carbon atoms which may have a substituent, a decyloxy group having 2 to 6 carbon atoms which may have a substituent, and a carbon number which may have a substituent a β-diketone group of 5 to 10 or a dimercaptomethyl group having a fluorenyl group having 1 to 6 carbon atoms which may have a substituent.

R ^{2 is} preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent. The k of the formula [I] is preferably 3.

R ^{3 is} preferably a halogen atom, NO ₃ , an alkoxy group having 1 to 6 carbon atoms which may have a substituent, a decyloxy group having 2 to 6 carbon atoms which may have a substituent, and a carbon number which may have a substituent a β-diketone group of 5 to 10 or a dimercaptomethyl group having a fluorenyl group having 1 to 6 carbon atoms which may have a substituent.

R ^{4 is} preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent. As M ¹ , a metal atom belonging to Group 4 of the periodic table is preferred, and titanium or zirconium is more preferred. When M ¹ is a metal atom belonging to Group 4 of the periodic table, m of the formula [II] is preferably 4.

However, although boron and strontium are classified as metalloids, they are included in the metal in this specification.

Examples of the compound (G1) include aluminum chloride, aluminum nitrate, aluminum acetate, ginseng (2,4-pentanedione) aluminum, trimethoxy aluminum, triethoxy aluminum, and tri-n-propoxy. a base aluminum, an aluminum triisopropoxide, a tri-n-butoxy aluminum, a tri-sec-butoxy aluminum, a tri-tert-butoxy aluminum, etc., more preferably an aluminum triisopropoxide and Tris-sec-butoxy aluminum. As the compound (G), two or more kinds of compounds (G1) can be used in combination.

Examples of the compound (G2) include bismuth (2,4-pentanedione) titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetra-n-butoxytitanium. a titanium compound such as ruthenium (2-ethylhexyloxy) titanium; ruthenium (2,4-pentanedione) zirconium, tetra-n-propoxy zirconium, tetra-n-butoxyzirconium, etc. Zirconium compounds and the like. These may be used alone or in combination of two or more compounds (G2).

As long as the effect of the present invention can be obtained, the compound (G) occupies The ratio of the compound (G1) is not particularly limited. The compound other than the compound (G1) (for example, the compound (G2)) is a ratio of the compound (G), and is, for example, preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol%. Below %, it can also be 0% by mole.

At least a part of the hydrolyzable characteristic group of the compound (G) is converted into a hydroxyl group by hydrolyzing the compound (G). Further, by condensing the hydrolyzate, a compound in which a metal atom (M) is bonded through an oxygen atom (O) is formed. When this condensation is repeated, a compound which can be substantially regarded as a metal oxide is formed. Further, a hydroxyl group is usually present on the surface of the metal oxide (C) thus formed.

In the present specification, a compound having a ratio of [the number of moles of oxygen atoms (0) bonded to a metal atom (M)/[the number of moles of metal atoms (M)] of 0.8 or more is contained in the metal oxidation. (C). Here, only the oxygen atom (O) bonded to the metal atom (M) is an oxygen atom (O) having a structure represented by MOM, such as an oxygen atom (O) represented by MOH, and a metal. Except for the oxygen atom to which the atom (M) and the hydrogen atom (H) are bonded. The above-mentioned ratio of the metal oxide (C) is preferably 0.9 or more, more preferably 1.0 or more, still more preferably 1.1 or more. Although the upper limit of the ratio is not particularly limited, when the atomic valence of the metal atom (M) is n, it is usually represented by n/2.

It is very important that the compound (G) has a hydrolyzable characteristic group due to the aforementioned hydrolysis condensation. When these groups are not bonded, the polymerization of the intended metal oxide (C) becomes difficult because the hydrolysis condensation reaction is not caused or is extremely slow.

The hydrolysis condensate of the compound (G) can be, for example, conventionally known The sol-gel method is manufactured from a specific raw material. In the raw material, a compound selected from the group consisting of a compound (G), a partial hydrolyzate of the compound (G), a complete hydrolyzate of the compound (G), and a compound (G), and a compound (G) can be used. At least one of the group consisting of a compound obtained by condensing a part of the complete hydrolyzate.

The metal oxide (C) to be mixed with the phosphorus compound (D)-containing material (containing the phosphorus compound (D) or the phosphorus compound (D)) preferably contains substantially no phosphorus atom.

[Phosphorus compound (D)]

The phosphorus compound (D) contains a site which can react with the metal oxide (C), and usually contains such a site in plural. In a preferred embodiment, the phosphorus compound (D) contains 2 to 20 such sites (atoms or functional groups). In the case of such a portion, a portion which exists on the surface of the metal oxide (C) and which can react with a functional group (for example, a hydroxyl group) is contained. For example, in such an example, a halogen atom directly bonded to a phosphorus atom or an oxygen atom directly bonded to a phosphorus atom is contained. These halogen atoms or oxygen atoms may cause a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (C). A functional group (for example, a hydroxyl group) present on the surface of the metal oxide (C) is usually bonded to a metal atom (M) constituting the metal oxide (C).

As the phosphorus compound (D), a structure having a halogen atom or an oxygen atom directly bonded to a phosphorus atom can be used. Such a phosphorus compound (D) can be bonded by condensation with a hydroxyl group (hydrolysis) present on the surface of the metal oxide (C). The phosphorus compound (D) may be one having one phosphorus atom, It may be one having two or more phosphorus atoms.

The phosphorus compound (D) may, for example, be a polyphosphoric acid selected from the group consisting of phosphoric acid, diphosphoric acid, triphosphoric acid, and a phosphoric acid of four or more molecules, phosphorous acid, phosphonic acid, phosphinic acid, phosphinic acid An oxoacid of phosphorus such as Phosphinic acid, phosphinic acid, or the like (such as sodium phosphate), and derivatives thereof (such as a halide (such as Phosphoryl chloride), At least one of the group consisting of an anhydrate (for example, phosphorus pentoxide).

These phosphorus compounds (D) may be used alone or in combination of two or more. Among these phosphorus compounds (D), phosphoric acid or phosphoric acid (D) other than phosphoric acid is preferably used alone. By using phosphoric acid, the stability of the coating liquid (T) described later and the gas barrier properties of the obtained multilayered structure are improved.

Layer (Z1) may comprise a specific polymer (F). The polymer (F) may be a polymer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a salt of a carboxyl group. The polymer (F) may be, for example, a polymer exemplified for the polymer (B). Further, the layer (Z1) may further contain other components than the polymer (F). Examples of the other component include those exemplified as the other components which can be contained in the layer (Y). The content of the other components in the layer (Z1) is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[Inorganic vapor deposited layer, layer (Z2), layer (Z3)]

The multilayer structure may comprise an inorganic evaporation layer. Such an inorganic deposited layer can be formed by vapor deposition of an inorganic substance. Examples of the inorganic substance include a metal (for example, aluminum), a metal oxide (for example, cerium oxide, aluminum oxide), a metal nitride (for example, tantalum nitride), a metal nitride oxide (for example, cerium oxynitride), or a metal carbonization. Nitride (for example, niobium carbonitride) or the like. Among these, the inorganic deposited layer formed of alumina, cerium oxide, magnesium oxide, or tantalum nitride is preferred from the viewpoint of excellent barrier properties against oxygen or water vapor. The layer (Z) in the multilayer structure of the present invention may be an inorganic vapor-deposited layer containing aluminum. For example, the layer (Z) may comprise a layer (Z2) which is an evaporation layer of aluminum and/or a layer (Z3) which is an evaporation layer of alumina. In one example, layer (Z) is layer (Z2) or layer (Z3).

The method for forming the inorganic deposited layer is not particularly limited, and a vacuum deposition method (for example, resistance heating vapor deposition, electron beam evaporation, molecular beam epitaxy, etc.), sputtering, or ion plating may be used. Physical vapor phase epitaxy, thermal chemical vapor epitaxy (eg, catalytic chemical vapor epitaxy), photochemical vapor epitaxy, plasma chemical vapor epitaxy (eg, capacitively coupled Plasma, inductively coupled plasma, surface wave plasma, electron cyclotron resonance (Electron cyclotron resonance), dual magnetron (Dual magnetron), atomic layer deposition, etc., organometallic vapor phase epitaxy, etc. Crystal method. Although the thickness of the inorganic deposited layer differs depending on the type of the components constituting the inorganic deposited layer, it is preferably in the range of 0.002 to 0.5 μm. In this range, the thickness of the multilayer structure may be selected to be good in barrier properties or mechanical properties. When the thickness of the inorganic vapor-deposited layer is less than 0.002 μm, the reproducibility of the barrier property of the inorganic vapor-deposited layer of oxygen or water vapor tends to be lowered, and the inorganic vapor-deposited layer may not exhibit sufficient barrier properties. condition. Moreover, when the thickness of the inorganic vapor-deposited layer exceeds 0.5 μm, when the multilayered structure is stretched or bent, the barrier property of the inorganic deposited layer tends to be lowered. The thickness of the inorganic deposited layer is more preferably in the range of 0.005 to 0.2 μm, and still more preferably in the range of 0.01 to 0.1 μm.

[Manufacturing method of multilayer structure]

An example of the method for producing the multilayer structure of the present invention will be described below. The matters described in the multilayer structure of the present invention can be applied to the manufacturing method described below, and thus the description thereof will be omitted. Further, the matters described in the production method can be applied to the multilayer structure of the present invention.

This manufacturing method is a manufacturing method of the multilayer structure of the base material (X) and the layer (Z) and the layer (Y). The manufacturing method includes a layer (Y) forming step and a layer (Z) forming step, and the layer (Y) forming step includes the step (Yi) of preparing a coating liquid (S) comprising the polymer (A) and a solvent. And a step (Y-ii) of forming a layer (Y) on the substrate (X) using the coating liquid (S). The step of forming the layer (Z) is described later. The coating liquid (S) may contain the polymer (B). When the coating liquid (S) contains the polymer (B), in the step (Y-i), the polymer (A) and the polymer (B) are mixed at a specific ratio by mass ratio. Thereby, the polymer (A) and the polymer (B) form a layer (Y) which is mixed at this ratio. The mass ratios of the polymer (A), the polymer (B), and the like are omitted as described above.

[Coating liquid (S)]

The solvent used in the coating liquid (S) is dependent on the polymer (A) (and the polymer) The type of (B)) may be appropriately selected, but is preferably water, an alcohol, or a mixed solvent of these.

The pH of the coating liquid (S) is preferably in the range of 0.1 to 6.0, more preferably in the range of 0.2 to 5.0, from the viewpoint of storage stability of the coating liquid (S) and gas barrier properties of the multilayer structure. More preferably, it is in the range of 0.5 to 4.0. The pH of the coating liquid (S) can be adjusted by a conventional method, for example, by adding an acidic compound or a basic compound.

Usually, in the step (Y-ii), the layer (Y) is formed by removing the solvent after applying the coating liquid (S). The method of applying the coating liquid (S) is not particularly limited, and a conventional method can be employed. Examples of the coating method include casting, dipping, roll coating, gravure coating, screen printing, reverse coating, spray coating, contact coating, die coating, and metering bars. Coating method, chamber doctor (Bag Doctor) and coating method, curtain coating method, bar coating method and the like.

The method for removing the solvent of the coating liquid (S) is not particularly limited, and a conventional drying method can be applied. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The drying temperature is preferably lower than the flow start temperature of the substrate (X) by from 0 to 15 °C.

[layer (Z) forming step]

The method for producing a multilayer structure includes a step of forming a layer (Z) containing aluminum atoms on a substrate (X). According to the layer (Z) forming step, a multilayer structure comprising the layer (Z) is obtained. Layer (Z) and layer (Y) are formed in an adjacent manner good.

The layer (Z) formation step can be carried out at any stage. For example, the layer (Z) forming step may be performed before the step (Yi), or may be performed after the step (Y-ii), although it may be carried out at any stage between the stages, but preferably in the step (Yi) Before proceeding. When the layer (Y) is disposed between the substrate (X) and the layer (Z), after the step (Y-ii), a layer (Z) forming step is performed. Further, when the layer (Z) is disposed between the substrate (X) and the layer (Y), the layer (Z) forming step is carried out before the step (Y-ii). At this time, in the step (Y-ii), the coating liquid (S) is applied onto the layer (Z).

When the layer (Z) is a layer (Z2) which is an evaporation layer of aluminum or a layer (Z3) which is an evaporation layer of alumina, the layers can be formed by the above-described general vapor deposition method. Therefore, the method of forming the layer (Z1) will be described in detail below. In addition, an example of the method of forming the layer (Z1) is described in Japanese Laid-Open Patent Publication No. 2013-208794.

When the layer (Z1) is formed, the layer (Z) forming step may include the steps (Z-i), (Z-ii), and (Z-iii). In the step (Z-i), the coating liquid (T) is prepared by mixing the metal oxide (C), the phosphorus compound (D) and the solvent. In the step (Z-ii), the coating layer (Z1) is formed on the substrate (X) by coating the coating liquid (T) on the substrate (X). In the step (Z-iii), the layer (Z1) is formed on the substrate (X) by heat-treating the precursor layer at a temperature of 110 ° C or higher. The details of the steps (Z-i) to (Z-iii) will be described later.

Each step is usually carried out in the order of step (Z-i), step (Z-ii), step (Z-iii), and step (Y-ii). However, when the layer (Y) is formed between the substrate (X) and the layer (Z1), the step (Y-ii) is carried out before the step (Z-ii) (which may be before the step (Z-i)). Also, steps can be implemented between step (Z-ii) and step (Z-iii) (Y-ii). From the viewpoint of obtaining a multilayer structure excellent in appearance, it is preferred to carry out the step (Y-ii) after the step (Z-iii).

[Step (Z-i)]

In the step (Z-i), the coating liquid (T) containing the metal oxide (C), the phosphorus compound (D) and the solvent is mixed. In one aspect, in the step (Z-i), the metal oxide (C) and the phosphorus compound (D) are allowed to react in a solvent. When the metal oxide (C), the phosphorus compound (D), and the solvent are mixed, other compounds (for example, the polymer (F)) may be present.

[Dispersion of Metal Oxide (C)]

When the metal oxide (C) is alumina, the preparation of the dispersion of alumina is firstly obtained by hydrolyzing and condensing the aluminum alkoxide by adding an acid to adjust the pH of the aqueous solution, if necessary, to obtain a slurry of alumina. . Next, a dispersion of alumina is obtained by degumming the slurry in the presence of a specific amount of acid. Further, a dispersion of a metal oxide (C) containing a metal atom other than aluminum can be produced by the same production method.

As the acid catalyst used for the hydrolysis condensation, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When an acid catalyst is used for the hydrolysis condensation, it is preferred to use an appropriate amount depending on the type of the acid so that the pH before the hydrolysis condensation is in the range of 2.0 to 4.0.

The step (Z-i) preferably comprises the following steps (Z-i-1) to (Z-i-3).

Step (Zi-1): a step of preparing a dispersion (J) containing a metal oxide (C), a step (Zi-2): a step of preparing a solution (K) containing the phosphorus compound (D), and a step (Zi- 3): a step of mixing the dispersion (J) and the solution (K) obtained in the steps (Zi-1) and (Zi-2).

The step (Z-i-2) can be carried out first than the step (Z-i-1), or simultaneously with the step (Z-i-1), or after the step (Z-i-1).

[Step (Z-i-1)]

In the step (Z-i-1), a dispersion (J) containing a metal oxide (C) is prepared. The dispersion (J) may be a dispersion of the metal oxide (C). The dispersion (J) can be condensed by condensation or hydrolysis, for example, according to a method employed in a conventional sol-gel method, for example, by mixing a compound (G), water, and, if necessary, an acid catalyst or an organic solvent. (G) Modulation. The dispersion of the metal oxide (C) obtained by condensation or hydrolysis condensation of the compound (G) can be directly used as the dispersion (J) containing the metal oxide (C), and if necessary, for the dispersion ( J) Perform a specific treatment (such as the aforementioned degumming or addition or subtraction of a solvent for concentration control). The solvent used in the step (Z-i-1) is not particularly limited, but is preferably an alcohol such as methanol, ethanol or isopropyl alcohol, water or a mixed solvent thereof. Further, the step (Z-i-1) may include a step of condensing (for example, hydrolyzing and condensing) at least one compound selected from the group consisting of the compound (G) and the compound (G).

[Step (Z-i-2)]

In the step (Z-i-2), a solution (K) containing the phosphorus compound (D) is prepared. The solution (K) is prepared by dissolving the phosphorus compound (D) in a solvent. When the solubility of the phosphorus compound (D) is low, the dissolution can be promoted by performing heat treatment or ultrasonic treatment.

The solvent used for the preparation of the solution (K) may be appropriately selected depending on the type of the phosphorus compound (D), but preferably contains water. The solvent may contain an organic solvent as long as it does not interfere with the dissolution of the phosphorus compound (D).

[Step (Z-i-3)]

In the step (Z-i-3), the dispersion (J) and the solution (K) are mixed. The coating liquid (T) may contain a polymer (F). Further, the coating liquid (T) may contain at least one acid compound (Q) selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary. The solution obtained in the step (Z-i-3) can be used as the coating liquid (T) as it is. In this case, the solvent contained in the dispersion (J) or the solution (K) is usually a solvent of the coating liquid (T). Further, in the solution obtained in the step (Z-i-3), a treatment such as addition of an organic solvent, preparation of a pH value, and addition of an additive may be used as a coating liquid (T).

The pH of the coating liquid (T) is preferably in the range of 0.1 to 6.0, more preferably in the range of 0.2 to 5.0, from the viewpoint of storage stability of the coating liquid (T) and gas barrier properties of the multilayer structure. More preferably, it is in the range of 0.5 to 4.0. The pH of the coating liquid (T) can be adjusted by a conventional method, for example, by adding an acidic compound or a basic compound.

[Step (Z-ii)]

In the step (Z-ii), a layer (Z1) precursor layer is formed on the substrate (X) by coating the coating liquid (T) on the substrate (X). The coating liquid (T) may be directly applied onto the surface of at least one side of the substrate (X), or may be applied to the substrate (X) through another layer. Further, before applying the coating liquid (T), the surface of the substrate (X) is treated with a conventional anchor coating agent, or a conventional adhesive is applied to the surface of the substrate (X), etc., and the substrate can be applied to the substrate. The surface of (X) forms an adhesion layer (L). Further, by coating the coating liquid (T) on the layer (Y) formed on the substrate (X) by the aforementioned step (Y-ii), the layer (Z1) can be formed in the layer before the layer (Y).

The coating liquid (T) at the time of the coating (Z-ii), the viscosity measured by a Brookfield-type rotational viscometer (the SB type viscometer: the rotor No. 3, the rotation speed of 60 rpm) was applied. The temperature at the time of cloth is preferably 3,000 mPa. Below s, more preferably 2,000mPa. s below. Further, as the viscosity of the coating liquid (S), it is preferably 50 mPa. Above s, more preferably 100mPa. Above s, more preferably 200mPa. s above. With this viscosity of 3,000mPa. In the following, the leveling property of the coating liquid (T) is improved, and a multilayer structure having a more excellent appearance can be obtained. The viscosity of the coating liquid (T) at the time of coating in the step (Z-ii) can be adjusted by the mixing time or the stirring strength after the mixing of the concentration, the temperature, and the step (Z-i-3). For example, it is possible to reduce the viscosity by performing the mixing after the mixing of the step (Z-i-3) for a long period of time. The method of applying the coating liquid (T) to the substrate (X) is not particularly limited, and a conventional method can be used. As the coating method, for example, a method of applying the coating liquid (S) in the step (Y-ii) can be mentioned.

Usually in the step (Z-ii), by removing the coating liquid (T) The solvent forms the precursor layer of layer (Z1). The method of removing the solvent is not particularly limited, and a conventional drying method can be applied. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The drying temperature is preferably lower than the flow start temperature of the substrate (X) by from 0 to 15 °C.

[Step (Z-iii)]

In the step (Z-iii), the layer (Z1) is formed by heat-treating the precursor layer (layer (Z1) precursor layer) formed in the step (Z-ii) at a temperature of 110 ° C or more.

In the step (Z-iii), the particles of the metal oxide (C) are mutually reacted by a phosphorus atom (phosphorus atom derived from the phosphorus compound (D)). From another viewpoint, in the step (Z-iii), a reaction for producing a reaction product (E) is carried out. In order to sufficiently carry out the reaction, the temperature of the heat treatment is preferably 110 ° C or higher, more preferably 140 ° C or higher, still more preferably 170 ° C or higher, and particularly preferably 190 ° C or higher. When the heat treatment temperature is low, the treatment time is increased in order to obtain a sufficient degree of reaction, which causes a decrease in productivity. The upper limit of the temperature at which the heat treatment is preferred varies depending on the type of the substrate (X) and the like. For example, when a thermoplastic resin film composed of a polyamide resin is used as the substrate (X), the temperature of the heat treatment is preferably 190 ° C or lower. Further, when a thermoplastic resin film composed of a polyester resin is used as the substrate (X), the temperature of the heat treatment is preferably 220 ° C or lower. The heat treatment can be carried out in an air atmosphere, a nitrogen atmosphere, an argon atmosphere or the like.

The heat treatment time is preferably in the range of 0.1 second to 1 hour. More preferably, it is in the range of 1 second to 15 minutes, and more preferably in the range of 5 to 300 seconds.

The method for producing a multilayer structure may include the step of irradiating ultraviolet rays to the precursor layer or layer (Z1) before the layer (Z1). The ultraviolet irradiation can be carried out at any stage after the step (Z-ii) (for example, after the solvent removal of the applied coating liquid (T) is almost completed).

The adhesive layer (L) is disposed between the substrate (X) and the layer (Z1), and the surface of the substrate (X) may be treated with a conventional anchor coating agent or coated before the coating liquid (T) is applied. A conventional adhesive is applied to the surface of the substrate (X).

The multilayer structure obtained in this manner can be directly used as the multilayer structure of the present invention. However, as the multilayer structure as described above, another member (for example, another layer or the like) may be further formed or formed as the multilayer structure of the present invention. This component can then be carried out by conventional methods.

[Next layer (L)]

In the multilayer structure of the present invention, the layer (Y) and/or the layer (Z) may be laminated directly in contact with the substrate (X). Further, the layer (Y) and/or the layer (Z) may be laminated to the substrate (X) through other layers. For example, layer (Y) and/or layer (Z) may be laminated to substrate (X) through an adhesive layer (L). According to this configuration, the adhesion between the substrate (X) and the layer (Y) and/or the layer (Z) can be improved. The layer (L) can then be formed with an adhesive resin. The adhesive layer (L) composed of the adhesive resin can be formed on the surface of the substrate (X) by treating the surface of the substrate (X) with a conventional anchor coating agent or by applying a conventional adhesive. As the binder, a 2-liquid reaction type polyamine in which a polyisocyanate component and a polyol component are mixed and reacted is preferred. An ethyl carbureate-based adhesive. Further, by adding a small amount of an additive such as a conventional decane coupling agent to the anchor coating agent or the adhesive, the adhesion can be further improved. The decane coupling agent may, for example, be a decane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amine group, a urea group or a fluorenyl group, but is not limited thereto. By strongly bonding the substrate (X) and the layer (Y) and/or the layer (Z) through the adhesive layer (L), it is more effective when the multilayer structure of the present invention is subjected to printing or lamination processing. The deterioration of the gas barrier property or the appearance is suppressed, and further, the drop strength of the packaging material using the multilayer structure of the present invention can be improved. The thickness of the layer (L) may be in the range of 0.01 to 10 μm, for example, in the range of 0.01 to 5 μm, or in the range of 0.01 to 1 μm, or in the range of 0.01 to 0.5 μm.

[other layers]

The multilayer structure of the present invention may comprise other layers for enhancing various properties, such as imparting heat sealability, or barrier properties or mechanical properties. In the multilayer structure of the present invention, for example, the layer (Y) and the layer (Z) are laminated directly to the substrate (X) or through the adhesive layer (L), and the other layer can be directly or transparently The layer (L) is then fabricated or formed. The other layer may, for example, be an ink layer or a polyolefin layer, but is not limited thereto. Further, these other layers may be replaced by a molded body composed of the material (for example, a molded body having a three-dimensional shape). The number of layers and the lamination order of the layers constituting the multilayer structure are not particularly limited. In a preferred embodiment of the multilayer structure, at least one of the substrate (X), the layer (Y), and the layer (Z) has a laminate of the substrate (X) / layer (Z) / layer (Y). structure.

The multilayer structure of the present invention may comprise an ink layer for printing a trade name or image. Such a multilayer structure of the present invention can be produced by directly forming the ink layer by directly laminating the layer (Y) and the layer (Z) directly after the substrate (X) or the adhesion layer (L). The ink layer may, for example, be a liquid-dried film in which a polyurethane resin containing a pigment (for example, titanium oxide) is dispersed in a solvent, but may be a polyurethane resin containing no pigment, Or a resist-dried film for forming an ink or an electronic circuit wiring using another resin as a main component. As a coating method of the ink layer of the layer (Y), various coating methods such as a wire bar, a spin coater, and a die coater can be used in addition to the gravure printing method. The thickness of the ink layer is preferably in the range of 0.5 to 10.0 μm, more preferably in the range of 1.0 to 4.0 μm.

The polymer (B) present in the layer (Y) has a hydroxy group and/or a carboxyl group having a high affinity with the subsequent layer (L) or other layers (for example, an ink layer or the like), the lift layer (Y) and the other The adhesion of the layers. Therefore, it is possible to maintain the adhesion between the layers after the treatment of the curved neck, and it is possible to suppress the appearance of the layering and the like.

By using the outermost layer of the multilayered structure of the present invention as the polyolefin layer, the multilayer structure can be provided with heat sealability or the mechanical properties of the multilayer structure can be improved. The polyolefin is preferably polypropylene or polyethylene from the viewpoints of heat sealability or improvement in mechanical properties and the like. Further, in order to improve the mechanical properties of the multilayered structure, it is preferred to laminate a group of films selected from the group consisting of a film composed of polyester, a film composed of polyamine, and a polymer containing a hydroxyl group. At least one film in the group. From the viewpoint of improvement in mechanical properties, as the polyester, polyethylene terephthalate is preferred as The polyamine, preferably nylon-6, is a hydroxyl group-containing polymer, preferably an ethylene-vinyl alcohol copolymer. A layer composed of an anchor coating or an adhesive may be provided between the layers if necessary.

Hereinafter, a structure in which a layer (Y) and a layer (Z) phase phosphine are laminated is referred to as a layer (YZ). The layer (Y) included in the layer (YZ) is usually disposed on the surface of the multilayer structure. Further, in the following, a multilayer film including the substrate (X) and the layer (YZ) laminated on the substrate (X) may be referred to as a barrier multilayer film. This barrier multilayer film is also one of the multilayer structures of the present invention. In the multilayer structure of the present invention, the polyolefin layer may be disposed on the surface of one side, or the layer (Y) may be disposed on the surface of the other side.

[Composition of multilayer structure]

Specific examples of the constitution of the multilayered structure of the present invention are shown below. Further, in the following specific examples, each layer may be replaced by a molded body composed of the material (for example, a molded body having a three-dimensional shape). Further, the multilayer structure may have an adhesive layer or other layer of the adhesive layer (L) or the like, but the description of the adhesive layer or other layers will be omitted in the following specific examples.

(1) layer (YZ) / polyester layer, (2) layer (YZ) / polyester layer / layer (YZ), (3) layer (YZ) / polyamine layer, (4) layer (YZ) / Polyamide layer/layer (YZ), (5) layer (YZ)/polyolefin layer, (6) layer (YZ)/polyolefin layer/layer (YZ), (7) layer (YZ)/hydroxyl-containing Polymer layer, (8) layer (YZ) / hydroxyl group-containing polymer layer / layer (YZ), (9) layer (YZ) / paper layer, (10) layer (YZ) / paper layer / layer (YZ), (11) Layer (YZ) / Inorganic vapor deposition layer / Polyester layer, (12) layer (YZ) / Inorganic vapor deposition layer / Polyamide layer, (13) layer (YZ) / Inorganic vapor deposition layer / Polyolefin layer, (14) layer (YZ) / inorganic vapor deposition layer / hydroxyl group-containing polymer layer, (15) layer (YZ) / polyester layer / polyamide layer / polyolefin layer, (16) layer (YZ) / polyester layer / layer ( YZ) / Polyimide layer / polyolefin layer, (17) Polyester layer / layer (YZ) / Polyamide layer / Polyolefin layer, (18) layer (YZ) / Polyamide layer / Polyester layer / Polyolefin layer, (19) layer (YZ) / polyamine layer / layer (YZ) / polyester layer / polyolefin layer, (20) polyamine layer / layer (YZ) / polyester layer / polyolefin layer , (21) layer (YZ) / polyolefin layer / polyamide layer / polyolefin layer, (22) layer (YZ) / polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer, (23 ) polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer, (24) layer (YZ) / polyolefin layer / polyolefin layer, (25) layer (YZ) / polyolefin layer / layer (YZ / polyolefin layer, (26) polyolefin layer / layer (YZ) / polyolefin layer, (27) layer (YZ) / polyester layer / polyolefin layer, (28) layer (YZ) / polyester layer / Layer (YZ) / polyolefin layer, (29) polyester layer / layer (YZ) / polyolefin Layer, (30) layer (YZ) / polyamine layer / polyolefin layer, (31) layer (YZ) / polyamine layer / layer (YZ) / polyolefin layer, (32) polyamine layer / layer (YZ) / polyolefin layer, (33) layer (YZ) / polyester layer / paper layer, (34) layer (YZ) / polyamide layer / paper layer, (35) layer (YZ) / polyolefin layer / paper layer, (36) polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyester layer / polyolefin layer, (37) polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyamine layer / polyolefin layer, (38) polyolefin layer / paper layer / Polyolefin layer/layer (YZ)/polyolefin layer, (39) paper layer/polyolefin layer/layer (YZ)/polyester layer/polyolefin layer, (40) polyolefin layer/paper layer/layer (YZ) / polyolefin layer, (41) paper layer / layer (YZ) / polyester layer / polyolefin layer, (42) paper layer / layer (YZ) / polyolefin layer, (43) layer (YZ) / paper layer / Polyolefin layer, (44) layer (YZ) / polyester layer / paper layer / polyolefin layer, (45) polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / hydroxyl group-containing polymerization Layer, (46) polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / polyamide layer, (47) polyolefin layer / paper layer / polyolefin layer / layer (YZ) / Polyolefin layer/polyester layer, (48) inorganic deposited layer/layer (YZ)/polyester layer, (49) inorganic deposited layer/layer (YZ)/polyester layer/layer (YZ)/inorganic vapor deposition Layer, (50) inorganic vapor deposited layer/layer (YZ)/polyamidamine layer, (51) inorganic deposited layer/layer (YZ)/polyamine layer/layer (YZ)/inorganic deposited layer, (52) inorganic steaming Plating/layer (YZ)/polyolefin layer, (53) inorganic deposited layer/layer (YZ)/polyolefin layer/layer (YZ)/inorganic deposited layer.

According to the present invention, a multilayer structure and an antistatic sheet having an oxygen permeability of 2 mL/(m ² .day.atm) or less at 20 ° C and 85% RH can be obtained. Further, a multilayer structure and an antistatic sheet having a moisture permeability of 1.0 g/(m ² /day) or less under conditions of 40 ° C and 90% RH can be obtained. The method of measuring the oxygen permeability and the moisture permeability and the measurement conditions are as described in the examples below.

[use]

The antistatic sheet of the present invention has high gas barrier properties and antistatic properties. Therefore, the antistatic sheet of the present invention can be applied to a wide variety of applications.

[Packaging material]

The packaging material of the present invention comprises the antistatic sheet of the present invention. The packaging material comprising the antistatic sheet of the present invention can be applied to a wide variety of applications. The packaging material preferably has an antistatic property as a necessary use in addition to the barrier property against oxygen or water vapor. For example, by the package of the present invention The material is preferably used as a packaging material for a powder such as dried squid or red pepper. Moreover, the packaging material of the present invention is preferably used as a packaging material for electronic components such as transistors, diodes, capacitors, and piezoelectric element recorders, in addition to food packaging materials.

The packaging material of the present invention is not particularly limited and can be produced by various methods known in the art. For example, a container (packaging material) can be produced by joining an antistatic sheet or a film material (hereinafter simply referred to as "film material") containing the antistatic sheet to form a specific container. Examples of the molding method include thermoforming, injection molding, and extrusion blow molding. Further, a container (packaging material) can be produced by forming a layer (Y) on the substrate (X) which is formed into a shape of a specific container. The container produced in this manner is sometimes referred to as a "packaging container" in this specification.

Further, the packaging material containing the antistatic sheet of the present invention can be used for secondary processing of various molded articles. Such a molded article (package) may be a vertical bag-filled sealed bag, a vacuum bag, a pouch, a laminated tube container, an infusion bag, a lid for a container, a paper container, or a vacuum heat insulator. The molded article of these can be heat-sealed. In this case, since the antistatic sheet of the present invention is less likely to adhere to suspended substances such as dust, it is possible to reduce the trapping of suspended matter during heat sealing.

[Vertical bag filling and sealing bag]

The packaging material of the present invention may be a vertical bag filling and sealing bag. An example will be shown in Fig. 1. The vertical form fill seal pouch 10 shown in Fig. 1 is an antistatic sheet 11 of the present invention, which is composed of two end portions 11a and a body portion 11b. The square is formed by sealing. The vertical form fill seal pouch 10 can be manufactured by a vertical form filling machine. The bag making by the vertical bag filling machine is applicable to a wide variety of methods, but in either method, the contents are supplied from the opening above the bag, and then the opening is sealed to make a vertical bag filling. sealed bag. The vertical form-filled sealed sealed bag is composed of, for example, a heat-sealed film material at the upper end, the lower end, and the side portions. The vertical form fill seal pouch of the packaging container of the present invention is excellent in gas barrier properties and water vapor barrier properties, and has less adhesion to dust or the like on the adhesive surface during bag making. Therefore, by filling the sealed bag with the vertical bag, it is possible to prevent deterioration of the quality of the contents for a long period of time.

[pocket]

The packaging material of the present invention may be a pouch. An example will be shown in Fig. 2. The flat bag 20 of Fig. 2 is formed by two sheets of the antistatic sheet 11 by the joint portions 11c being joined to each other. In the present specification, the phrase "pocket" means a container mainly comprising a food material, a daily necessities or a pharmaceutical product as a content, and a film material as a wall member. For example, the shape and use of the pouch can be exemplified by a spout bag, a Chuck seal pouch, a flat pouch, a stand-up pouch, and a lateral system. The bag is filled with a sealed pouch, a curved neck pouch, and the like. The pouch can be formed by laminating a barrier multilayer film with at least one other layer. The pouch of the packaging container of the present invention is excellent in gas barrier properties and water vapor barrier properties, and has less adhesion to dust or the like on the adhesive surface during bag making. Therefore, by using the pouch, it is possible to prevent deterioration of the quality of the contents for a long period of time. Also, in one of the bags For example, since the transparency can be maintained, it is easy to confirm the contents or to confirm the deterioration of the contents due to deterioration.

[vacuum heat insulator]

The vacuum heat-dissipating system includes a covering material and a heat-dissipating body disposed in a core material surrounded by the covering material, and the inside of the core material is decompressed. The vacuum heat insulator is a heat-dissipating property equivalent to the heat-dissipating property of the heat-insulating body composed of the urethane foam, and can be achieved by a thinner and lighter heat-dissipating body. Since the vacuum heat insulator of the present invention can maintain the heat-dissipating effect over a long period of time, it can be used for the heat-dissipating material, the wall portion, the patio portion, and the roof portion of the home appliance such as a refrigerator, a hot water supply device, and a rice cooker. It is used for heat insulation of household heat-dissipating materials, vehicle roofing materials, heat-dissipating panels such as vending machines, and heat-moving machines such as heat pump applications.

One example of the vacuum heat insulator of the present invention is shown in Fig. 3. The vacuum heat insulator 30 of Fig. 3 includes a covering material 11 and a particulate core material 31, and the covering material 11 is composed of two film materials joined by the peripheral portion 11c, and the core material 31 is disposed by the coating. The interior of the material 11 is surrounded. In the central portion surrounded by the peripheral portion 11c, the covering member 11 functions as a partition wall for isolating the inside and the outside of the core member 31, and is closely adhered to the core member 31 by the pressure between the inside and the outside.

The material and shape of the core material are not particularly limited as long as they are suitable for heat removal. Examples of the core material include perlite powder, cerium oxide powder, precipitated cerium oxide powder, diatomaceous earth, calcium silicate, glass wool, rock wool, artificial (synthetic) wool, and resin foam (for example, benzene). Ethylene foam, urethane Ester foam) and the like. As the core material, a hollow container, a honeycomb structure or the like which is formed into a specific shape can also be used.

[electronic device]

An example of an electronic device having the antistatic sheet of the present invention will be described. A partial cross-sectional view of an electronic device is shown in FIG. The electronic device 40 of FIG. 4 includes an electronic device body 41, a sealing material 42 for sealing the electronic device body 41, and a protective sheet (antistatic sheet) 43 for protecting the surface of the electronic device body 41. The sealing material 42 covers the entire surface of the electronic device body 41. The protective sheet 43 is attached to the surface of the electronic device body 41 side and is disposed through the sealing material 42. A protective sheet 43 may be disposed on the surface opposite to the surface on which the protective sheet 43 is disposed. In this case, the protective sheet disposed on the surface on the opposite side may be the same as or different from the protective sheet 43.

The electronic device body 41 is not particularly limited, and is, for example, a photoelectric conversion device such as a solar battery, an organic EL display, an information display device such as a liquid crystal display or an electronic paper, or an illumination device such as an organic EL light-emitting device. The sealing material 42 is an optional member that is appropriately added in accordance with the type and use of the electronic device body 41. Examples of the sealing material 42 include an ethylene-vinyl acetate copolymer or polyvinyl butyral. The protective sheet 43 may be disposed so as to protect the surface of the electronic device body 41, and may be disposed directly on the surface of the electronic device body 41, or may be disposed on the surface of the electronic device body 41 through other members such as the sealing material 42.

A preferred example of the electronic device body 41 is a solar cell. Examples of the solar cell include a lanthanide solar cell, a compound semiconductor solar cell, and an organic thin film solar cell. Examples of the lanthanoid solar cell include a single crystal germanium solar cell, a polycrystalline germanium solar cell, and an amorphous germanium solar cell. Examples of the compound semiconductor solar cell include a III-V compound semiconductor solar cell, a II-VI compound semiconductor solar cell, and an I-III-VI compound semiconductor solar cell. Examples of the organic thin film solar cell include a pn junction organic thin film solar cell, a Bulk heterojunction organic thin film solar cell, and the like. Further, the solar cell may be a solar cell in which a plurality of unit cells are connected in series, or may be a solar cell of a stacked shape.

The electronic device body 41 can also be fabricated by a Roll To Roll method depending on the type thereof. In the winding process, a flexible substrate (for example, a stainless steel substrate or a resin substrate) that is wound around a transfer roller is fed, and an electronic device body 41 is formed by forming an element on the substrate. The electronic device body 41 is wound. Roll winding. At this time, the protective sheet 43 also has a form of a sheet having a long length of flexibility, and more specifically, it can be prepared as a sheet of a long-length sheet wound body. In one example, the protective sheet 43 fed from the transporting roller is laminated on the electronic device body 41 wound around the winding roller, and is wound together with the electronic device body 41. In another example, the electronic device body 41 wound around the winding roller is fed out from the roller and laminated with the protective sheet 43. In a preferred embodiment of the invention, the electronic device itself is flexible.

The protective sheet 43 contains the antistatic sheet of the present invention. Defense The electrostatic sheet can be composed only of a multilayer structure. Alternatively, the antistatic sheet may comprise a multilayer structure, and other members (eg, other layers) of the laminated multilayer structure. The protective sheet 43 is not particularly limited in thickness and material as long as it is a layered laminate suitable for protection of the surface of an electronic device, and includes the above-described antistatic sheet.

The antistatic sheet of the present invention can be made transparent by forming an antistatic sheet from a transparent substrate and a transparent layer. Further, the antistatic sheet of the present invention has high barrier properties against oxygen or water vapor, and further has antistatic properties. Especially when the antistatic sheet of the present invention is used for a product such as a solar cell member or a display member, this property sometimes contributes greatly to the durability of the article.

The protective sheet 43 may, for example, also include a surface protective layer disposed on one surface or both side surfaces of the antistatic sheet. As the surface protective layer, a layer composed of a resin which is not easily damaged is preferable. Further, a surface protective layer of a device which can be used outdoors in a solar cell is preferably made of a resin having high weather resistance (for example, light resistance). Further, when it is necessary to transmit the surface of the light, it is preferably a surface protective layer having a high light transmittance. Examples of the material of the surface protective layer (surface protective film) include poly(meth)acrylate, polycarbonate, polyethylene terephthalate, polyethylene-2,6-naphthalate, and poly. Vinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymerization (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and the like. One example of the protective sheet includes a layer disposed on one side (Meth) acrylate layer.

In order to improve the durability of the surface protective layer, various additives (for example, ultraviolet absorbers) may be added to the surface protective layer. A preferred example of the surface protective layer having high weather resistance is an acryl-based resin layer to which an ultraviolet absorber is added. Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, but are not limited thereto. And so on. Further, other stabilizers, light stabilizers, antioxidants, and the like may be used in combination.

As long as the effects of the present invention can be exerted, the present invention encompasses various aspects of the above-described configurations within the scope of the technical scope of the present invention.

[Examples]

In the following, the present invention is not limited by the examples, but the invention is not limited to the embodiments, and many variations are possible in the technical idea of the present invention. The analysis and evaluation of the following examples and comparative examples were carried out as follows. Still, for the analysis and evaluation of the comparative example, the layer (Y) is sometimes replaced with a layer (CY).

(1) Determination of infrared absorption spectrum

The measurement was performed by attenuated total reflection using a Fourier transform infrared spectrophotometer. The measurement conditions are as follows.

Device: Spectrum One by Perkin Elmer

Measurement mode: attenuated total reflection method

Measurement area: 800~1,400cm ^-1

(2) Determination of the thickness of each layer

The multilayer structure was cut using a converging ion beam (FIB) to prepare a section for observation of a cross section (thickness: 0.3 μm). The prepared chips were fixed on a sample stand with a carbon ribbon, and platinum ion plating was performed for 30 seconds at an acceleration voltage of 30 kV. The cross section of the multilayer structure was observed using a field emission type transmission electron microscope, and the thickness of each layer was calculated. The measurement conditions are as follows.

Device: JEM-2100F manufactured by JEOL Ltd.

Acceleration voltage: 200kV

Magnification: 250,000 times

(3) Determination of oxygen transmission rate

The multilayer structure was placed in an oxygen permeation amount measuring device on the side of the carrier gas so as to face the layer of the substrate, and the oxygen permeability was measured. The measurement conditions are as follows.

Device: MOCON OX-TRAN2/20 by Modern Controls

Temperature: 20 ° C

Oxygen supply side humidity: 85% RH

Humidity on the carrier gas side: 85% RH

Oxygen pressure: 1 air pressure

Carrier gas pressure: 1 air pressure

(4) Determination of moisture permeability

The multilayer structure was placed in a water vapor transmission amount measuring device so that the carrier gas side faced the substrate layer, and the moisture permeability (water vapor transmission rate) was measured. The measurement conditions are as follows.

Device: MOCON PERMATRAN 3/33 by Modern Controls

Temperature: 40 ° C

Humidity on the water supply side: 90% RH

Humidity on the carrier gas side: 0% RH

(5) Determination of surface electrical resistance value

Among the surfaces of the multilayer structure, a surface on the opposite side to the substrate (X) is in contact with a specific electrode, and the electrode is connected to a digital ultra-high resistance/micro current meter. Further, according to JIS K 6911 (2006) and JIS C2139 (2008), a voltage was applied between the main electrode and the protective electrode, and the surface electrical resistance of the surface layer of the layer (Y) and the comparative example was measured. The measurement conditions are as follows. Further, the surface electrical resistivity was calculated by multiplying the value of the obtained surface electrical resistance by the upper electrode coefficient of 18.84.

Device: R8340A by Advantest Co., Ltd.

Temperature: 20 ° C

Voltage: 500V

Main electrode diameter: 50mm

Protective electrode inner diameter: 70mm

(6) Adhesion of dust

After the flour is attached to the surface of the multilayer structure, air is quickly blown to remove the flour on the surface. After the removal, the case where the unattached flour was evaluated was evaluated as A, except that the case of slight adhesion was evaluated as B, and the case of excessive adhesion was evaluated as C.

<Production Example of Coating Liquid (T-1)>

230 parts by mass of distilled water was stirred and heated to 70 °C. In the distilled water, 88 parts by mass of aluminum triisopropoxide was dropped over 1 hour, and the liquid temperature was gradually raised to 95 ° C, and the isopropyl alcohol produced by distillation was subjected to hydrolysis condensation. 4.0 parts by mass of a 60% by mass aqueous solution of nitric acid was added to the obtained liquid, and the aggregate of the particles of the hydrolyzed condensate was degummed by stirring at 95 ° C for 3 hours. Then, the liquid was concentrated so that the solid content concentration was 10% by mass in terms of alumina. With respect to 18.66 parts by mass of the dispersion thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 5% by mass of a polyvinyl alcohol aqueous solution (PVA124 manufactured by Kuraray Co., Ltd.; saponification degree: 98.5 mol%, viscosity average) were added. The degree of polymerization was 2,400, and the viscosity of 4% by mass of the aqueous solution at 20 ° C was 60 mPa·s) of 0.50 parts by mass, and the mixture was stirred to obtain a dispersion. Next, the dispersion was stirred while maintaining the liquid temperature at 15 ° C, and 3.65 parts by mass of an 85% by mass aqueous phosphoric acid solution was dropped to have a viscosity of 1,500 mPa. St. stirring was continued at 15 ° C to obtain the desired coating liquid (T-1). In the coating liquid (T-1), the molar ratio of the aluminum atom to the phosphorus atom is an aluminum atom: phosphorus atom = 1.15: 1.00.

<Synthesis Example of Polymer (A-1)>

Under a nitrogen atmosphere, 10 g of vinylphosphonic acid and 0.025 g of 2,2'-azobis(2-methylamidinopropane) 2 hydrochloride were dissolved in 5 g of water, and stirred at 80 ° C for 3 hours. After cooling, 15 g of water was added to the polymerization solution for dilution, and the mixture was filtered using a cellulose film, Spectra/Por (registered trademark) manufactured by Spectrum Laboratories. After distilling off the water in the filtrate, the polymer (A-1) was obtained by vacuum drying at 50 ° C for 24 hours. The polymer (A-1) is a poly(vinylphosphonic acid). As a result of GPC analysis, the number average molecular weight of the polymer was 10,000 in terms of polyethanol.

<Synthesis Example of Polymer (A-2)>

Under a nitrogen atmosphere, 9.5 g of vinylphosphonic acid, 0.40 g of methacrylic acid and 0.025 g of 2,2'-azobis(2-methylamidinopropane) 2 hydrochloride were dissolved in 5 g of water and stirred at 80 ° C. 3 hours. After cooling the polymerization solution, 15 g of water was added to the polymerization solution for dilution, and then filtered using a cellulose film, Spectra/Por (registered trademark) manufactured by Spectrum Laboratories. After the water in the filtrate was distilled off, it was dried by vacuum at 50 ° C for 24 hours to obtain a polymer (A-2). The polymer (A-2) is a copolymer of vinylphosphonic acid and methacrylic acid (molar ratio vinylphosphonic acid: methacrylic acid = 95:5). As a result of GPC analysis, the number average molecular weight of the polymer was 9,500 in terms of polyethanol.

<Synthesis Example of Polymer (CA-1)>

Under a nitrogen atmosphere, 8.5 g of 2-phosphonooxyethyl methacrylate and 0.1 g of azobisisobutyronitrile were dissolved in 17 g of methyl ethyl ketone, and the mixture was stirred at 80 ° C for 12 hours. After cooling the obtained polymer solution, 170 g of 1,2-dichloroethane was added, and the polymer was recovered as a precipitate by decantation. Next, the polymer was dissolved in tetrahydrofuran, and 1,2-dichloroethane was used as a poor solvent to carry out reprecipitation purification. After performing reprecipitation purification three times, a polymer (CA-1) other than the polymer (A) was obtained by vacuum drying at 50 ° C for 24 hours. The polymer (CA-1) is a polymer of 2-phosphoniumoxyethyl methacrylate. As a result of GPC analysis, the number average molecular weight of the polymer was 10,000 in terms of polystyrene.

<Production Example of Coating Liquid (S-1)>

The polymer (A-1) obtained in the above Synthesis Example was dissolved in a mixed solvent of water and methanol (water: methanol = 7:3 by mass ratio) to obtain a coating liquid having a solid content concentration of 1% by mass ( S-1).

<Production Example of Coating Liquid (S-2)>

The coating liquid (S-2) was obtained in the same manner as in the production of the coating liquid (S-1) except that the polymer (A-1) was replaced with the polymer (A-2).

<Production Example of Coating Liquid (S-3)>

65% by mass of the polymer (A-1) obtained in the above Synthesis Example, polyvinyl alcohol (PVA124 manufactured by Kuraray Co., Ltd.; saponification degree: 98.5 mol%; viscosity average degree of polymerization 2,400, 4 mass at 20 ° C) % aqueous solution viscosity 60mPa. s) a mixture of 35% by mass. This mixture was dissolved in a mixed solvent of water and methanol (water: methanol = 7:3 by mass ratio) to obtain a coating liquid (S-3) having a solid content concentration of 1% by mass.

<Production Example of Coating Liquid (S-4)>

80% by mass of the polymer (A-1) obtained in the above Synthesis Example, polyvinyl alcohol (PVA124 manufactured by Kuraray Co., Ltd.; saponification degree: 98.5 mol%, viscosity average degree of polymerization 2,400, and mass at 20 ° C) % aqueous solution viscosity 60 mPa.s) 20% by mass of a mixture. This mixture was dissolved in a mixed solvent of water and methanol (water: methanol = 7:3 by mass ratio) to obtain a coating liquid (S-4) having a solid content concentration of 1% by mass.

<Production Example of Coating Liquid (CS-1)>

The coating liquid (CS-1) was obtained in the same manner as in the production of the coating liquid (S-1) except that the polymer (A-1) was replaced with the polymer (CA-1).

<Example 1>

First, as the base material (X), a "polymirror (registered trademark) P60" (thickness: 12 μm) (hereinafter also referred to as PET12) manufactured by Toray Industries Co., Ltd., which is a polyethylene terephthalate film, is prepared. On the substrate, the coating liquid (T-1) was applied to a substrate having a thickness of 0.3 μm after drying using a bar coater. The coated film was dried at 110 ° C for 5 minutes and then heat treated at 160 ° C for 1 minute to form a layer (Z1) on the substrate. In this manner, a structure having a structure of a so-called base material (X) / layer (Z1) was obtained. As a result of measuring the infrared absorption spectrum of the obtained structure, the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 was 1,108 cm ^-1 , and the half-value width of the maximum absorption band was 37 cm ^-1 . Next, the coating liquid (S-1) was applied to the above-mentioned structure so that the thickness after drying became 0.05 μm by a bar coater, and the layer (Y) was formed by drying at 220 ° C for 1 minute. In this manner, a multilayer structure (1-1) having a structure of a substrate (X) / layer (Z1) / layer (Y) was obtained.

The oxygen permeability and the moisture permeability of the obtained multilayered structure (1-1) were measured by the above methods. Further, with respect to the obtained multilayer structure (1-1), the surface electrical resistivity of the layer (Y) was measured by the above method.

<Example 2>

In the same manner as in the production of the multilayer structure (1-1) of Example 1, except that the coating liquid (S-1) was changed to the coating liquid (S-2), a multilayer structure (2-1) was produced. ).

<Example 3>

The multilayer structure (Example 1-1) of Example 1 was changed except that the coating liquid (S-1) was changed to the coating liquid (S-3), and the thickness of the layer (Y) after drying was changed to 0.01 μm. The production was carried out in the same manner, and a multilayer structure (3-1) was produced.

<Example 4>

The multilayer structure (1-1) of Example 1 except that the substitution layer (Z1) was formed into a layer (Z3) of alumina having a thickness of 0.03 μm by a vacuum evaporation method. The production was carried out in the same manner, and a multilayer structure (4-1) was produced.

<Example 5>

On the PET 12 of the substrate (X), a layer (Z3) of alumina having a thickness of 0.03 μm was formed by a vacuum evaporation method. Next, a layer (Z1) was formed on the layer (Z3) in the same manner as in Example 1 using the coating liquid (T-1). Next, a layer (Y) was formed on the layer (Z1) in the same manner as in Example 1 using the coating liquid (S-1). In this manner, a multilayer structure (5-1) having a structure of a substrate (X) / layer (Z3) / layer (Z1) / layer (Y) was produced.

<Example 6>

A layer (Z1) was formed on the PET 12 of the substrate (X) using the coating liquid (T-1) in the same manner as in Example 1. Next, a layer (Z3) of alumina having a thickness of 0.03 μm was formed on the layer (Z1) by a vacuum evaporation method. Next, a layer (Y) was formed on the layer (Z3) in the same manner as in Example 1 using the coating liquid (S-1). In this manner, a multilayer structure (6-1) having a structure of a substrate (X) / layer (Z1) / layer (Z3) / layer (Y) was produced.

<Example 7>

The multilayer structure (1-1) of Example 1 was changed except that the coating liquid (S-1) was changed to the coating liquid (S-4), and the thickness of the layer (Y) after drying was changed to 0.01 μm. The production was carried out in the same manner, and a multilayer structure (7-1) was produced.

<Comparative Examples 1 to 3>

In Comparative Example 1, a multilayer structure (C1-1) was produced in the same manner as in the production of the multilayer structure (1-1) of Example 1, except that the coating liquid (S-1) was not used. In Comparative Example 2, the coating liquid (S-1) was changed to the coating liquid (CS-1), and the production was carried out in the same manner as in the production of the multilayer structure (1-1) of Example 1. Multilayer structure (C2-1) of the structure of the substrate (X) / layer (Z1) / layer (CY). In Comparative Example 3, a multilayer structure (C3-1) was produced in the same manner as in the production of the multilayer structure (4-1) of Example 4, except that the coating liquid (S-1) was not used.

The manufacturing conditions of the multilayered structures of the examples and the comparative examples are shown in Table 1. In the table, "A: B" means "polymer (A): polymer (B)".

The multilayer structures of the multilayer structures (2-1) to (7-1) and the comparative examples (C1-1) to (C3-1) of the examples were evaluated in the same manner as the multilayer structures (1-1). The evaluation results of the multilayer structure are shown in Table 2.

As shown in the above Table 2, the surface of the antistatic sheet of the present invention has a low electrical resistivity. Therefore, the antistatic sheet of the present invention exhibits high antistatic performance and greatly reduces the amount of dust adhering due to static electricity.

<Example 8>

An adhesive layer was formed on the obtained multilayered structure (1-1), and a linear short-chain branched polyethylene (also referred to as a linear low-density polyethylene (LLDPE)) film (thickness: 50 μm) was laminated on the adhesive layer. The mixture was allowed to stand at 40 ° C for 5 days for aging. In this manner, a multilayer structure (1-2) having a structure of a so-called base material (X) / layer (Z1) / layer (Y) / adhesive layer / linear short-chain branched polyethylene film was obtained. In the linear short-chain branched polyethylene film, "Uni-LuxLS-711C" (trademark) manufactured by Idemitsu Unitech Co., Ltd. was used. The above-mentioned adhesive layer was formed by applying a two-component type adhesive to a thickness of 3 μm after drying using a bar coater. 2-liquid type adhesive "A-520" (trademark) of "Takelac" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-50" (trademark) of "TAKENATE" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-liquid reaction type polyurethane-based adhesive composed of the above.

The multilayer structure (1-2) was cut into a width of 100 mm, and the linear short-chain branched polyethylene film layers were brought into contact with each other to be supplied to a vertical form filling and packaging machine (manufactured by Orihiro Co., Ltd.) by heat sealing. The vertical bag-filling and sealing bag (1-3) (width 40 mm, length 120 mm) is prepared by a vertical bag filling and packaging machine. Evaluate the dust adhesion inside the vertical bag-filled sealed bag (1-3). The results are shown in Table 3.

<Examples 9 to 14>

A vertical bag-filled sealed bag was produced in the same manner as in Example 8 except that the multilayer structure (1-1) of Example 8 was used instead of the multilayer structure (2-1) to (7-1). 2-3)~(7-3), evaluate the internal dust adhesion. The results are shown in Table 3.

<Comparative Examples 4 to 6>

A vertical bag-filled sealed pouch was prepared in the same manner as in Example 8 except that instead of using the multilayer structure (C1-1) to (C3-1), the multilayer structure (1-1) of Example 8 was used. C1-3)~(C3-3), evaluate the internal dust adhesion. The results are shown in Table 3.

As shown in the above Table 3, the antistatic sheet provided with the multilayer structure of the present invention exhibits high antistatic performance and greatly reduces the amount of dust adhering due to static electricity.

[Industrial availability]

The present invention can be utilized in an antistatic sheet, and a packaging material and an electronic device including the same. According to the present invention, an antistatic sheet excellent in gas barrier properties and water vapor barrier properties and excellent in antistatic property can be obtained. Therefore, the antistatic sheet of the present invention is preferably used as a packaging material for foods, pharmaceuticals, medical equipment, industrial materials, electronic equipment, and the like. Moreover, it is preferable to use a display member such as a substrate film for a liquid crystal display, a substrate film for an organic EL, a substrate film for an electronic paper, a sealing film for an electronic device, or a film for a plasma display panel; a film for an LED, and a film for an IC label Electronic device related members such as a solar cell module such as a solar cell module, a solar cell back sheet, and a protective film for a solar cell; a member for optical communication, a flexible film for an electronic device, a separator for a fuel cell, and a sealing film for a fuel cell An electronic device such as a substrate film of various functional films.

Claims (8)

An antistatic sheet characterized by comprising an antistatic sheet comprising a multilayer structure comprising a substrate (X), a layer (Z) containing aluminum atoms, and a layer (Y), the layer (Y) The polymer (A) having a phosphonic acid unit is contained, and the surface electrical resistivity of the layer (Y) is 1.0 × 10 ⁶ Ω/sq or more and 4.0 × 10 ¹³ Ω/sq or less. The antistatic sheet according to claim 1, wherein the polymer (A) having a phosphonic acid unit is a polymer (Aa) having a vinylphosphonic acid unit. An antistatic sheet according to claim 1 or 2, wherein at least one of said layer (Z) and said layer (Y) are disposed adjacent to each other. The antistatic sheet according to any one of claims 1 to 3, wherein the layer (Z) is provided with a layer (Z1) containing a reaction product (E), and the reaction product (E) is a metal containing aluminum atoms. a reaction product obtained by reacting an oxide (C) with a phosphorus compound (D). In the infrared absorption spectrum of the layer (Z1), the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 is 1,080 to 1,130 cm ^- The scope of ¹ . The antistatic sheet according to any one of claims 1 to 4, wherein the layer (Z) is provided with a vapor deposited layer (Z3) of alumina. The antistatic sheet according to any one of claims 1 to 5, wherein the oxygen permeability is 2 mL/(m ² .day.atm) or less at 20 ° C and 85% RH. A packaging material comprising the antistatic sheet according to any one of claims 1 to 6. An electronic device comprising the antistatic sheet according to any one of claims 1 to 6.